Hydroprocessing catalysts and methods for making thereof

Abstract

A method to upgrade heavy oil feedstock using an ebullated bed reactor and a novel catalyst system is provided. The ebullated bed reactor system includes two different catalyst with different characteristics: an expanded catalyst zone containing particulate catalyst having a particle size of greater than 0.65 mm; and a slurry catalyst having an average particle size ranging from 1 to 300 μm. The slurry catalyst is introduced to the ebullated bed system with the heavy oil feedstock, and entrained in the upflowing hydrocarbon liquid passing through the ebullated bed reaction zone. The slurry catalyst reduces the formation of sediment and coke precursors in the ebullating bed reactor system. The slurry catalyst is prepared from at least a water-soluble metal precursor and pre-sulfided prior to being introduced with the heavy oil feedstock to the reactor system, or sulfided in-situ in the ebullated bed reactor in another embodiment.

The invention claimed is:  
     
       1. A dual catalyst system for use in a heavy oil upgrade process, the catalyst system comprises:
 a particulate catalyst for use in an expanded catalyst zone of an ebullated bed reactor to produce an upgraded heavy oil; 
 a pre-sulfided slurry catalyst having an average particle size ranging from 1 to 300 μm in a hydrocarbon oil diluent which is not heavy oil feedstock, prepared from a solution comprising at least a water-soluble metal precursor salt of a Primary metal selected from Group VIB metals and Group VIII metals, and sulfided by a sulfiding agent which is not heavy oil feedstock under sulfiding conditions at a molar ratio of sulfur to metal of at least 1.5:1; 
 wherein the slurry catalyst upon being introduced into the ebullated bed reactor with a heavy oil feedstock is carried through the expanded catalyst zone and reduces formation of sediments and coke formation in the ebullated bed system. 
 
     
     
       2. The dual catalyst system of  claim 1 , wherein the sulfidation under sulfiding conditions forming the slurry catalyst is ex-situ prior to introducing the slurry catalyst into the ebullated bed reactor. 
     
     
       3. The dual catalyst system of  claim 1 , wherein the Primary metal is molybdenum and wherein the water-soluble metal precursor salt is selected from the group of molybdates, alkali metal heptamolybdates, alkali metal orthomolybdates, alkali metal isomolybdates, phosphomolybdic acid, molybdenum oxide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdic acid, and mixtures thereof. 
     
     
       4. The dual catalyst system of  claim 1 , wherein the solution further comprises at least a water-soluble metal precursor salt of a Promoter metal selected from any of a Group IVB metal, Group VIII metal, and Group IIB metal, and wherein the Promoter metal is different from the Primary metal and the Promoter metal is added at a weight ratio of Promoter metal to Primary metal of 1-50 wt. % to promote the slurry catalyst. 
     
     
       5. The dual catalyst system of  claim 4 , wherein the solution comprising at least a water-soluble metal precursor salt of a Primary metal and at least a water-soluble metal precursor of a Promoter metal is sulfided by a sulfiding agent under sulfiding conditions at a molar ratio of sulfur to metal of at least 1.5:1 to co-sulfide the Primary metal and the Promoter metal. 
     
     
       6. The dual catalyst system of  claim 4 , wherein the solution comprising at least a water-soluble metal precursor salt of a Primary metal is sulfided by a sulfiding agent under sulfiding conditions at a molar ratio of sulfur to metal of at least 1.5:1 prior to the addition of the water-soluble metal precursor salt of a Promoter metal to the solution. 
     
     
       7. The dual catalyst system of  claim 4 , wherein the solution comprising at least a water-soluble metal precursor salt of a Promoter metal is sulfided by a sulfiding agent under sulfiding conditions at a molar ratio of sulfur to metal of at least 1.5:1 prior to being added to the water-soluble metal precursor salt of a Primary metal. 
     
     
       8. The dual catalyst system of  claim 4 , wherein the water-soluble metal precursor salt of a Primary metal and the water-soluble metal precursor salt of a Promoter metal are separately sulfided prior to being combined forming a solution. 
     
     
       9. The dual catalyst system of  claim 4 , wherein the Primary metal is molybdenum and wherein the water-soluble metal precursor salt of the Primary metal is selected from the group of molybdates, alkali metal heptamolybdates, alkali metal orthomolybdates, alkali metal isomolybdates, phosphomolybdic acid, molybdenum oxide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdic acid, and mixtures thereof. 
     
     
       10. The dual catalyst system of  claim 4 , wherein the Promoter metal is nickel and wherein the water-soluble metal salt of the Promoter metal is selected from the group of nickel acetate, nickel carbonate, nickel chloride, nickel sulfate, nickel nitrate, nickel acetylacetone, nickel citrate, nickel oxalate, and mixtures thereof. 
     
     
       11. The dual catalyst system of  claim 1 , wherein the slurry catalyst is prepared from at least a solution comprising at least a water-soluble metal precursor salt of a Primary metal, sulfided by a sulfiding agent under sulfiding conditions at a molar ratio of sulfur to metal of at least 1.5:1, and further reduced in a transformation step by mixing with a hydrocarbon diluent. 
     
     
       12. The dual catalyst system of  claim 11 , wherein the hydrocarbon diluent is selected from gasoline, diesel, vacuum gas oil (VGO), cycle oil (MCO or HCO), jet oil, fuel oil, and mixtures thereof. 
     
     
       13. The dual catalyst system of  claim 1 , wherein the slurry catalyst has an average particle size of at least 2 μm. 
     
     
       14. The dual catalyst system of  claim 1 , wherein the slurry catalyst has an internal pore volume ranging from 0.5 cm 3 /g to 1.8 cm 3 /g. 
     
     
       15. The dual catalyst system of  claim 1 , wherein the slurry catalyst has a polymodal pore size distribution with at least a first mode having at least 80% pore sizes ranging from 5 to 2000 Angstroms. 
     
     
       16. The dual catalyst system of  claim 1 , wherein the slurry catalyst has at least 30% of pore sizes of at least 100 Angstrom in diameter.